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WO2019021818A1 - High strength fiber composite material cable - Google Patents

High strength fiber composite material cable Download PDF

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Publication number
WO2019021818A1
WO2019021818A1 PCT/JP2018/026124 JP2018026124W WO2019021818A1 WO 2019021818 A1 WO2019021818 A1 WO 2019021818A1 JP 2018026124 W JP2018026124 W JP 2018026124W WO 2019021818 A1 WO2019021818 A1 WO 2019021818A1
Authority
WO
WIPO (PCT)
Prior art keywords
high strength
thermoplastic resin
fiber composite
resin
matrix resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/026124
Other languages
French (fr)
Japanese (ja)
Inventor
幸仁 山本
拓哉 片山
俊次 蜂須賀
倉地　育夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kensyu & Co Ltd
Tokyo Rope Manufacturing Co Ltd
Original Assignee
Kensyu & Co Ltd
Tokyo Rope Manufacturing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kensyu & Co Ltd, Tokyo Rope Manufacturing Co Ltd filed Critical Kensyu & Co Ltd
Priority to BR112020001384-6A priority Critical patent/BR112020001384A2/en
Priority to EP18837792.3A priority patent/EP3660209A4/en
Publication of WO2019021818A1 publication Critical patent/WO2019021818A1/en
Priority to US16/751,276 priority patent/US20200157738A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/165—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber inlay
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/165—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber inlay
    • D07B1/167—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber inlay having a predetermined shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
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    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
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    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
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    • E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
    • H01B7/182—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring comprising synthetic filaments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C—CHEMISTRY; METALLURGY
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    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
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    • D07B2201/104—Rope or cable structures twisted
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    • D07—ROPES; CABLES OTHER THAN ELECTRIC
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Definitions

  • the present invention relates to high strength fiber composite cables.
  • a high-strength fiber composite cable made by bundling multiple long high-strength fibers into a bundle and impregnating this into a resin has high tensile strength, low stretchability, is lightweight, is excellent in corrosion resistance, and is excellent in corrosion resistance It is widely used for bridges, concrete structures, transmission lines, etc.
  • thermoplastic resins are attracting attention from the viewpoint of mass productivity and the like (see, for example, WO 2001/051730).
  • Thermoplastic resins have lower fluidity at the time of melting than thermosetting resins, and are less likely to be impregnated into fiber bundles. If the thermoplastic resin is insufficiently impregnated, the fibers may be broken or intertwined to cause a disorder of the fibers, and the surface of the cable may be roughened. In addition, when voids are generated internally due to insufficient impregnation of the thermoplastic resin, the tensile strength of the cable is reduced, and the quality of the cable is reduced.
  • thermoplastic resin In order to sufficiently impregnate the thermoplastic resin into the fiber bundle, it is sufficient to improve the flowability of the thermoplastic resin, and it is conceivable to lower the viscosity of the thermoplastic resin as one method for improving the flowability of the thermoplastic resin .
  • the molecular weight of the thermoplastic resin may be reduced. However, if the molecular weight of the thermoplastic resin is reduced, the tensile strength of the high strength fiber composite cable produced by impregnating the fiber bundle with the same also decreases.
  • the viscosity of the thermoplastic resin can also be lowered by mixing the plasticizer with the thermoplastic resin.
  • bleed out a phenomenon in which the plasticizer comes to the surface over time
  • the plasticizer may not be uniformly dispersed in the thermoplastic resin (not compatible), and large droplets may be formed.
  • An object of the present invention is to sufficiently impregnate a high strength fiber bundle with a thermoplastic resin to thereby improve the mechanical strength of the cable.
  • Another object of the present invention is to fully impregnate a high strength fiber bundle with a thermoplastic resin, thereby providing a high quality cable.
  • the present invention is a high strength fiber composite cable in which a bundle of high strength fibers is impregnated with a matrix resin, and the matrix resin has an organic compound having a phenolic hydroxyl group and a glycidyl ether group in a thermoplastic resin. It is characterized in that it is a mixture of oligomers having a weight-average molecular weight of less than 10,000 obtained by reacting an organic compound.
  • a cable can also be called a rod, a rope, a rod etc., and means the thing whose length in the longitudinal direction is long compared with the area of a cross section.
  • the high strength fiber bundle constituting the high strength fiber composite cable typically refers to a bundle of a plurality of synthetic fiber filaments (wires) having a tensile strength of 20 g / d (259 kg / mm 2 ) or more.
  • the matrix resin obtained by mixing an oligomer having a weight average molecular weight of less than 10,000 obtained by reacting a thermoplastic resin with an organic compound having a phenolic hydroxyl group and an organic compound having a glycidyl ether group has a viscosity, The viscosity is lower than the viscosity of the thermoplastic resin, and thus the fluidity is higher than that of the base thermoplastic resin.
  • the matrix resin can be more easily impregnated into the bundle of high strength fibers as compared with the base material thermoplastic resin.
  • High strength fiber composite cables made by impregnating high strength fiber bundles with matrix resin compared to conventional high strength fiber composite cables made by impregnating thermoplastic resin into high strength fiber bundles It was confirmed by the test that the tensile strength is improved.
  • the matrix resin thermoplastic resin contained in the matrix resin
  • the matrix resin is sufficiently impregnated into the high strength fiber bundle, and the high strength fiber is firmly gripped by the fully impregnated matrix resin, and the generation of voids is also suppressed. It is considered that the tensile strength of the cable could be improved by
  • the matrix resin can be said to be a low viscosity thermoplastic resin because the viscosity is lowered while maintaining the properties of the thermoplastic resin.
  • the oligomer is kept at a concentration of less than 30% by weight.
  • concentration of oligomers occupying the matrix resin is too high, the tensile strength may be lower than conventional cables made by impregnating thermoplastic resin into bundles of high strength fibers. . This is because the concentration of the thermoplastic resin which occupies the matrix resin is relatively lowered and diluted by increasing the concentration of the oligomer, and the viscosity of the matrix resin becomes too low, for example, from the bundle of high strength fibers It is thought that it is due to flowing down.
  • the effect of improving the tensile strength of the cable which is caused by the thermoplastic resin contained in the matrix resin being fully impregnated into the high strength fiber bundle, can be It can be made to exceed the reduction effect of the tensile strength of the cable caused by the flow of the resin, and the cable can exhibit at least the same tensile strength as the conventional cable.
  • the occurrence of voids inside the cable is surely reduced, and the roughening of the cable surface is also suppressed, so a cable of higher quality than the conventional cable is provided.
  • thermoplastic resin polyphenylene sulfide, polyphenylene ether, a fluorine-containing resin, or an amide group-containing resin can be used.
  • Carbon fibers can be used for the high strength fibers.
  • the fiber volume content V f is 30% or more and less than 85%.
  • the interaction between the high strength fibers and the matrix resin comprising the thermoplastic resin can improve the tensile strength of the cable.
  • the method for producing a high-strength fiber composite cable according to the present invention comprises: reacting a thermoplastic resin with an oligomer having a weight-average molecular weight of less than 10,000 obtained by reacting an organic compound having a phenolic hydroxyl group and an organic compound having a glycidyl ether group.
  • the matrix resin having a melt flow rate improved by 1.5 to 50 times the melt flow rate of the thermoplastic resin, which is produced by mixing a predetermined amount, is heated to melt, and the molten matrix resin is converted into a bundle of high strength fibers. A bundle of high strength fibers impregnated and impregnated with matrix resin is drawn out.
  • the matrix resin can be sufficiently impregnated into the bundle of high strength fibers as compared with the thermoplastic resin.
  • the viscosity of the matrix resin can be adjusted by the amount of oligomers mixed.
  • FIG. 2 is an enlarged cross-sectional view of the carbon fiber composite cable taken along line II-II in FIG. It is a graph which shows the result of the tensile breaking strength test of a carbon fiber composite material cable. It is a graph which shows the relationship between the density
  • FIG. 1 shows the appearance of a carbon fiber composite cable.
  • FIG. 2 shows an enlarged cross-sectional view of the carbon fiber composite cable taken along line II-II of FIG.
  • a carbon fiber composite cable 1 is obtained by bundling a large number of long carbon fibers 2 in a circular cross section, impregnating the same with a matrix resin 3 and then curing the matrix resin 3.
  • the whole contains several tens of thousands to hundreds of thousands of carbon fibers (single fibers, filaments) 2.
  • the volume ratio (fiber volume content) V f of the carbon fibers 2 in the entire volume is generally 30% or more and less than 85%.
  • the carbon fiber composite cable 1 is produced, for example, by bundling about 6 to 7 tows in which about 12,000 carbon fibers 2 are bundled, impregnating the tow with the matrix resin 3 and curing it.
  • the carbon fiber composite cable 1 may be one in which all the carbon fibers 2 contained therein are aligned in one direction in the longitudinal direction as illustrated, or a plurality of tows are twisted together. It is also good.
  • the carbon fiber composite cable 1 may be configured of one tow (core wire) extending in one direction in the longitudinal direction and a plurality of tow (lateral lines) twisted around the one.
  • the diameter of the carbon fiber composite cable 1 can be arbitrarily adjusted by the number of carbon fibers 2 constituting the carbon fiber composite cable 1.
  • the matrix resin 3 is a mixture of a thermoplastic resin and an oligomer shown below, whereby the viscosity of the matrix resin 3 is made lower than the viscosity of the thermoplastic resin as the base material to improve the fluidity. It is.
  • the thermoplastic resin of the base material polyphenylene sulfide, polyphenylene ether, fluorine-containing resin (such as tetrafluoroethylene), and amide group-containing resin (such as polyamide) can be used.
  • an oligomer to be mixed one obtained by reacting an organic compound having a phenolic hydroxyl group (for example, a novolak type phenol resin) and an organic compound having a glycidyl ether group (for example, a phenyl glycidyl ether) is used.
  • an organic compound having a phenolic hydroxyl group for example, a novolak type phenol resin
  • an organic compound having a glycidyl ether group for example, a phenyl glycidyl ether
  • the matrix resin 3 is solid at normal temperature, melts by applying heat, and solidifies by cooling, so it can be said to be a thermoplastic resin, but it can be said as a thermoplastic resin. It is distinguished at least in viscosity from plastic resins (such as polyphenylene sulfide).
  • the viscosity of the thermoplastic resin as a base material for obtaining the matrix resin 3 is about 10 g / 10 min to 30 g / 10 min in melt flow rate, and the viscosity of the matrix resin 3 is much lower than this.
  • oligomer one having a weight average molecular weight of less than 10,000 is used.
  • weight average molecular weight exceeds 10,000, the compatibility between the thermoplastic resin and the oligomer decreases.
  • an oligomer having a weight average molecular weight of 5,000 or less is preferable to use an oligomer having a weight average molecular weight of 5,000 or less.
  • the weight average molecular weight of the oligomers can typically be adjusted by temperature control.
  • FIG. 3 is a graph showing the results of a tensile breaking strength test of a carbon fiber composite cable 1 (hereinafter referred to as a test object) having a fiber volume content V f of 50% and a diameter of 2.5 mm.
  • the horizontal axis shows the concentration (unit: wt%) of the oligomer contained in the matrix resin 3
  • the vertical axis shows the tensile breaking strength of the test object (unit: kN / mm 2 ).
  • the test sample is made by adhering powdery matrix resin 3 to a carbon fiber tow, collecting the six tow with the matrix resin 3 adhered on a drawing die heated to 330 ° C. to form a carbon fiber bundle.
  • the matrix resin 3 was melted by heating and drawn from a drawing die.
  • the matrix resin 3 impregnates the carbon fiber bundle at the drawing die.
  • the matrix resin 3 melted in advance may be attached to the tow, or the fibrous matrix resin 3 may be bundled with the tow.
  • a carbon fiber composite cable impregnated with a thermoplastic resin not mixed with an oligomer was also prepared, and a tensile breaking strength test was also conducted for comparison.
  • FIG. 4 is a graph showing the relationship between the concentration of oligomers contained in the matrix resin 3 (unit: wt%) and the melt flow rate (MFR) (unit: g / 10 min) of the matrix resin 3.
  • Melt flow rate was measured according to the procedure of JIS K 7210. The melt flow rate of the thermoplastic resin not mixed with the oligomer was also measured.
  • the melt flow rate can be used as an index indicating the viscosity of the sample, the higher the melt flow rate, the lower the viscosity of the sample (the more easily it flows), and the lower the viscosity, the higher the viscosity of the sample (the less flowable).
  • polyphenylene ether resin manufactured by Tosoh Corporation
  • thermoplastic resin polyphenylene ether resin
  • oligomer one obtained by reacting and stabilizing novolac type phenol resin (manufactured by Asahi Organic Materials Co., Ltd.) with phenyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was adopted.
  • novolak type phenol resin and phenyl glycidyl ether were reacted under predetermined temperature conditions, it was possible to make the weight average molecular weight of the oligomer less than 10,000.
  • the matrix resin 3 obtained by mixing the above-described oligomer with the polyphenylene ether resin is that the melt flow rate is surely increased (the viscosity is decreased), and the mixed polymer is It was confirmed that the melt flow rate rises sharply by increasing the amount. That is, the viscosity of the matrix resin 3 in which the above-described oligomer is mixed with the thermoplastic resin is surely reduced.
  • the cable in which the carbon fiber bundle is impregnated with the matrix resin 3 has a tensile fracture compared to the cable in which the carbon fiber bundle is impregnated with the thermoplastic resin (in which the oligomer concentration is 0 wt%). It was confirmed that the strength could be improved.
  • the matrix resin 3 has a lower viscosity than the thermoplastic resin, and hence the carbon fiber bundle is sufficiently impregnated with the matrix resin 3 (thermoplastic resin contained in the matrix resin). It is thought that it is because it can.
  • the above-mentioned oligomers do not at least greatly reduce the molecular weight of the thermoplastic resin, because the tensile strength at break is sufficiently increased.
  • a matrix resin 3 having a melt flow rate improved 1.5 to 50 times the melt flow rate of the thermoplastic resin is used.
  • By increasing the melt flow rate of the matrix resin 3 by 1.5 times or more from the melt flow rate of the thermoplastic resin it is possible to prevent breakage (roughness) of the carbon fibers 2 in the cable surface in the above-described drawing process, and (The step of bundling a plurality of tows into one and impregnating the matrix resin 3) can be facilitated.
  • the tensile strength of the cable can be maintained at least equal to that of the conventional cable.

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Abstract

L'objet de la présente invention est d'imprégner suffisamment un faisceau de fibres à haute résistance avec une résine thermoplastique sans affecter la résistance mécanique. Un câble de matériau composite à fibres à haute résistance est fabriqué par imprégnation d'un faisceau de fibres de carbone avec une résine matricielle. La résine matricielle est obtenue en mélangeant une résine thermoplastique, par exemple du sulfure de polyphénylène, avec un oligomère ayant un poids moléculaire moyen en poids inférieur à 10 000 obtenu par la mise à réagir d'un composé organique contenant un groupe hydroxyle phénolique et un composé organique contenant un groupe éther glycidylique. La résine matricielle a une viscosité inférieure à celle de la résine thermoplastique mère, et peut pénétrer facilement et de manière fiable le faisceau de fibres de carbone.The object of the present invention is to sufficiently impregnate a high-strength fiber bundle with a thermoplastic resin without affecting the strength. A high strength fiber composite material cable is made by impregnating a carbon fiber bundle with a matrix resin. The matrix resin is obtained by mixing a thermoplastic resin, for example polyphenylene sulfide, with an oligomer having a weight average molecular weight of less than 10,000 obtained by reacting an organic phenolic hydroxyl group-containing compound and a organic compound containing a glycidyl ether group. The matrix resin has a lower viscosity than the parent thermoplastic resin, and can easily and reliably penetrate the carbon fiber bundle.

Description

高強度繊維複合材ケーブルHigh strength fiber composite cable

　この発明は高強度繊維複合材ケーブルに関する。 The present invention relates to high strength fiber composite cables.

　複数本の長尺の高強度繊維を束にまとめ，これに樹脂を含浸させることでつくられる高強度繊維複合材ケーブルは，引張強度が高く，伸縮性が低く，また軽量であり，耐食性に優れているので，橋梁，コンクリート構造物，送電線などに広く用いられつつある。 A high-strength fiber composite cable made by bundling multiple long high-strength fibers into a bundle and impregnating this into a resin has high tensile strength, low stretchability, is lightweight, is excellent in corrosion resistance, and is excellent in corrosion resistance It is widely used for bridges, concrete structures, transmission lines, etc.

　繊維束に含浸する樹脂として，量産性等の観点から熱可塑性樹脂が注目されている（たとえばＷＯ２００１／０５１７３０参照）。 As a resin to be impregnated into fiber bundles, thermoplastic resins are attracting attention from the viewpoint of mass productivity and the like (see, for example, WO 2001/051730).

　熱可塑性樹脂は，熱硬化性樹脂に比べて溶融時の流動性が低く，繊維束に含浸させにくい。熱可塑性樹脂の含浸が不足すると，繊維が切れたり絡み合ったりして繊維の並びに乱れが生じ，ケーブルの表面が粗れてしまう。また，熱可塑性樹脂の含浸不足によって内部にボイドが発生すると，ケーブルの引張強度が低下し，ケーブルの品質が低下する。 Thermoplastic resins have lower fluidity at the time of melting than thermosetting resins, and are less likely to be impregnated into fiber bundles. If the thermoplastic resin is insufficiently impregnated, the fibers may be broken or intertwined to cause a disorder of the fibers, and the surface of the cable may be roughened. In addition, when voids are generated internally due to insufficient impregnation of the thermoplastic resin, the tensile strength of the cable is reduced, and the quality of the cable is reduced.

　熱可塑性樹脂を繊維束に十分に含浸するには熱可塑性樹脂の流動性を向上させればよく，熱可塑性樹脂の流動性を向上させる一つの手法として熱可塑性樹脂の粘度を下げることが考えられる。 In order to sufficiently impregnate the thermoplastic resin into the fiber bundle, it is sufficient to improve the flowability of the thermoplastic resin, and it is conceivable to lower the viscosity of the thermoplastic resin as one method for improving the flowability of the thermoplastic resin .

　熱可塑性樹脂の粘度を下げるには熱可塑性樹脂の分子量を低下させればよい。しかしながら熱可塑性樹脂の分子量を低下させるとそれを繊維束に含浸させることでつくられる高強度繊維複合材ケーブルの引張強度も低下してしまう。 In order to reduce the viscosity of the thermoplastic resin, the molecular weight of the thermoplastic resin may be reduced. However, if the molecular weight of the thermoplastic resin is reduced, the tensile strength of the high strength fiber composite cable produced by impregnating the fiber bundle with the same also decreases.

　可塑剤を熱可塑性樹脂に混合することで，熱可塑性樹脂の粘度を下げることもできる。しかしながら，ブリードアウト（時間の経過によって可塑剤が表面に浮き出てくる現象）が発生しやすくなり，これは高強度繊維複合材ケーブルをたとえばコンクリート構造物の補強材として用いるときの接着不良を生じさせる。さらに，熱可塑性樹脂の分子量と可塑剤の分子量が大きく相違すると，可塑剤が熱可塑性樹脂に均一に分散せず（相溶せず），大きな液滴となることがある。 The viscosity of the thermoplastic resin can also be lowered by mixing the plasticizer with the thermoplastic resin. However, bleed out (a phenomenon in which the plasticizer comes to the surface over time) tends to occur, which causes adhesion failure when using a high strength fiber composite cable as a reinforcing material for a concrete structure, for example. . Furthermore, if the molecular weight of the thermoplastic resin and the molecular weight of the plasticizer are largely different, the plasticizer may not be uniformly dispersed in the thermoplastic resin (not compatible), and large droplets may be formed.

　この発明は，高強度繊維束に熱可塑性樹脂を十分に含浸させ，これによりケーブルの機械的強度を向上させることを目的とする。 An object of the present invention is to sufficiently impregnate a high strength fiber bundle with a thermoplastic resin to thereby improve the mechanical strength of the cable.

　この発明はまた，高強度繊維束に熱可塑性樹脂を十分に含侵させ，これにより高品質のケーブルを提供することを目的とする。 Another object of the present invention is to fully impregnate a high strength fiber bundle with a thermoplastic resin, thereby providing a high quality cable.

　この発明は，高強度繊維の束にマトリックス樹脂を含浸させた高強度繊維複合材ケーブルであって，上記マトリックス樹脂が，熱可塑性樹脂に，フェノール性水酸基を有する有機化合物とグリジシルエーテル基を有する有機化合物とを反応させて得られる重量平均分子量10,000未満のオリゴマーを混合させたものであることを特徴とする。ケーブルは，ロッド，ロープ，棒などと呼ぶこともでき，横断面の面積に比べて長手方向の長さが長いものを意味する。高強度繊維複合材ケーブルを構成する高強度繊維束は，典型的には引張強度が20ｇ／ｄ（259kg／mm2）以上の合成繊維製フィラメント（素線）を複数本束ねたものを指す。 The present invention is a high strength fiber composite cable in which a bundle of high strength fibers is impregnated with a matrix resin, and the matrix resin has an organic compound having a phenolic hydroxyl group and a glycidyl ether group in a thermoplastic resin. It is characterized in that it is a mixture of oligomers having a weight-average molecular weight of less than 10,000 obtained by reacting an organic compound. A cable can also be called a rod, a rope, a rod etc., and means the thing whose length in the longitudinal direction is long compared with the area of a cross section. The high strength fiber bundle constituting the high strength fiber composite cable typically refers to a bundle of a plurality of synthetic fiber filaments (wires) having a tensile strength of 20 g / d (259 kg / mm 2 ) or more.

　熱可塑性樹脂にフェノール性水酸基を有する有機化合物とグリジシルエーテル基を有する有機化合物とを反応させて得られる重量平均分子量10,000未満のオリゴマーを混合させることで得られるマトリックス樹脂は，その粘度が，母材である熱可塑性樹脂の粘度に比べて低くなり，したがって母材である熱可塑性樹脂よりも流動性が高くなる。マトリックス樹脂は，母材である熱可塑性樹脂に比べて高強度繊維の束に確実に含浸しやすくなる。 The matrix resin obtained by mixing an oligomer having a weight average molecular weight of less than 10,000 obtained by reacting a thermoplastic resin with an organic compound having a phenolic hydroxyl group and an organic compound having a glycidyl ether group has a viscosity, The viscosity is lower than the viscosity of the thermoplastic resin, and thus the fluidity is higher than that of the base thermoplastic resin. The matrix resin can be more easily impregnated into the bundle of high strength fibers as compared with the base material thermoplastic resin.

　マトリックス樹脂を高強度繊維の束に含浸することでつくられる高強度繊維複合材ケーブルは，熱可塑性樹脂を高強度繊維の束に含浸することでつくられる従来の高強度繊維複合材ケーブルに比べて，引張強度が向上することが試験によって確認された。マトリックス樹脂（マトリックス樹脂に含まれる熱可塑性樹脂）が高強度繊維の束に十分に含浸し，十分に含侵したマトリックス樹脂によって高強度繊維が強固に把持され，またボイドの発生も抑制され，これらによってケーブルの引張強度を向上できたものと考えられる。マトリックス樹脂は，熱可塑性樹脂の性質を維持しつつその粘度を低下させたものであるので，低粘度熱可塑性樹脂と言うこともできる。 High strength fiber composite cables made by impregnating high strength fiber bundles with matrix resin compared to conventional high strength fiber composite cables made by impregnating thermoplastic resin into high strength fiber bundles , It was confirmed by the test that the tensile strength is improved. The matrix resin (thermoplastic resin contained in the matrix resin) is sufficiently impregnated into the high strength fiber bundle, and the high strength fiber is firmly gripped by the fully impregnated matrix resin, and the generation of voids is also suppressed. It is considered that the tensile strength of the cable could be improved by The matrix resin can be said to be a low viscosity thermoplastic resin because the viscosity is lowered while maintaining the properties of the thermoplastic resin.

　好ましくは，熱可塑性樹脂に上記オリゴマーを混合することによってつくられるマトリックス樹脂において，上記オリゴマーは30wt％未満の濃度にとどめられる。マトリックス樹脂を占めるオリゴマーの濃度を高くしすぎると，熱可塑性樹脂を高強度繊維の束に含浸することでつくられる従来ケーブルよりも引張強度が低くなることがあることが試験によって確認されたからである。これは，オリゴマーの濃度を高くすることによってマトリックス樹脂を占める熱可塑性樹脂の濃度が相対的に低められて希釈化されることや，マトリックス樹脂の粘度が低くなりすぎ，たとえば高強度繊維の束から流れ落ちてしまうことに起因すると考えられる。オリゴマーの濃度を30wt％未満にとどめることで，マトリックス樹脂に含まれる熱可塑性樹脂が高強度繊維の束に十分に含浸されることによって生じるケーブルの引張強度の向上作用を，上述した希釈化やマトリックス樹脂の流れ落ちによって生じるケーブルの引張強度の低減作用よりも上回らせることができ，従来ケーブルと少なくとも同等の引張強度を発揮するケーブルとすることができる。もっとも，機械的強度が同等であっても，ケーブル内部のボイドの発生が確実に低下し，ケーブル表面の粗れも抑制されるので，従来ケーブルよりも高品質のケーブルは提供される。 Preferably, in a matrix resin made by mixing the oligomer with a thermoplastic resin, the oligomer is kept at a concentration of less than 30% by weight. Tests have shown that if the concentration of oligomers occupying the matrix resin is too high, the tensile strength may be lower than conventional cables made by impregnating thermoplastic resin into bundles of high strength fibers. . This is because the concentration of the thermoplastic resin which occupies the matrix resin is relatively lowered and diluted by increasing the concentration of the oligomer, and the viscosity of the matrix resin becomes too low, for example, from the bundle of high strength fibers It is thought that it is due to flowing down. By keeping the concentration of the oligomer at less than 30 wt%, the effect of improving the tensile strength of the cable, which is caused by the thermoplastic resin contained in the matrix resin being fully impregnated into the high strength fiber bundle, can be It can be made to exceed the reduction effect of the tensile strength of the cable caused by the flow of the resin, and the cable can exhibit at least the same tensile strength as the conventional cable. However, even with the same mechanical strength, the occurrence of voids inside the cable is surely reduced, and the roughening of the cable surface is also suppressed, so a cable of higher quality than the conventional cable is provided.

　上記熱可塑性樹脂には，ポリフェニレンサルファイド，ポリフェニレンエーテル，フッ素含有樹脂，またはアミド基含有樹脂を用いることができる。高強度繊維には炭素繊維を用いることができる。 As the thermoplastic resin, polyphenylene sulfide, polyphenylene ether, a fluorine-containing resin, or an amide group-containing resin can be used. Carbon fibers can be used for the high strength fibers.

　好ましくは，繊維体積含有率Ｖｆが30％以上85％未満である。高強度繊維と熱可塑性樹脂を含むマトリックス樹脂との相互作用によってケーブルの引張強度を向上させることができる。 Preferably, the fiber volume content V f is 30% or more and less than 85%. The interaction between the high strength fibers and the matrix resin comprising the thermoplastic resin can improve the tensile strength of the cable.

　この発明による高強度繊維複合材ケーブルの製造方法は，熱可塑性樹脂に，フェノール性水酸基を有する有機化合物とグリジシルエーテル基を有する有機化合物とを反応させて得られる重量平均分子量10,000未満のオリゴマーを所定量混合することによってつくられる，上記熱可塑性樹脂のメルトフローレートよりも 1.5～50倍向上したメルトフローレートを持つマトリックス樹脂を加熱して溶融し，溶融したマトリックス樹脂を高強度繊維の束に含浸し，マトリックス樹脂が含浸した高強度繊維の束を引抜成形する。 The method for producing a high-strength fiber composite cable according to the present invention comprises: reacting a thermoplastic resin with an oligomer having a weight-average molecular weight of less than 10,000 obtained by reacting an organic compound having a phenolic hydroxyl group and an organic compound having a glycidyl ether group. The matrix resin having a melt flow rate improved by 1.5 to 50 times the melt flow rate of the thermoplastic resin, which is produced by mixing a predetermined amount, is heated to melt, and the molten matrix resin is converted into a bundle of high strength fibers. A bundle of high strength fibers impregnated and impregnated with matrix resin is drawn out.

　マトリックス樹脂の粘度は母材である熱可塑性樹脂の粘度よりも低いので，熱可塑性樹脂に比べてマトリックス樹脂は高強度繊維の束に十分に含浸させることができる。マトリックス樹脂の粘度は混合するオリゴマーの量によって調整することができる。熱可塑性樹脂のメルトフローレートよりも 1.5～50倍向上したメルトフローレートを持つマトリックス樹脂を用いることによって，高強度繊維の束を容易に集束することができるようになり，引抜成型における表面の繊維切れも防止することができる。さらに従来ケーブルと少なくとも同等の引張強度を達成することができる。高品質の高強度繊維複合材ケーブルを製造することができる。 Since the viscosity of the matrix resin is lower than the viscosity of the thermoplastic resin as the base material, the matrix resin can be sufficiently impregnated into the bundle of high strength fibers as compared with the thermoplastic resin. The viscosity of the matrix resin can be adjusted by the amount of oligomers mixed. By using a matrix resin having a melt flow rate that is 1.5 to 50 times better than the melt flow rate of a thermoplastic resin, it is possible to easily bundle a bundle of high strength fibers, and surface fibers in pultrusion molding It can also prevent breakage. Furthermore, at least equivalent tensile strength to conventional cables can be achieved. High quality high strength fiber composite cables can be manufactured.

炭素繊維複合材ケーブルの正面図である。It is a front view of a carbon fiber composite material cable. 図１のII－II線に沿う炭素繊維複合材ケーブルの拡大断面図である。FIG. 2 is an enlarged cross-sectional view of the carbon fiber composite cable taken along line II-II in FIG. 炭素繊維複合材ケーブルの引張破断強度試験の結果を示すグラフである。It is a graph which shows the result of the tensile breaking strength test of a carbon fiber composite material cable. マトリックス樹脂に含まれるオリゴマーの濃度とマトリックス樹脂のメルトフローレートとの関係を示すグラフである。It is a graph which shows the relationship between the density | concentration of the oligomer contained in matrix resin, and the melt flow rate of matrix resin.

　図１は炭素繊維複合材ケーブルの外観を示している。図２は図１のII－II線に沿う炭素繊維複合材ケーブルの拡大断面図を示している。 FIG. 1 shows the appearance of a carbon fiber composite cable. FIG. 2 shows an enlarged cross-sectional view of the carbon fiber composite cable taken along line II-II of FIG.

　炭素繊維複合材ケーブル１は，多数本の長尺の炭素繊維２を断面円形に束ね，これにマトリックス樹脂３を含浸させ，その後にマトリックス樹脂３を硬化させたもので，炭素繊維複合材ケーブル１の全体に数万本から数十万本の炭素繊維（単繊維，フィラメント）２が含まれている。炭素繊維複合材ケーブル１は，その全体積に占める炭素繊維２の体積割合（繊維体積含有率）Ｖｆが一般に30％以上85％未満とされる。 A carbon fiber composite cable 1 is obtained by bundling a large number of long carbon fibers 2 in a circular cross section, impregnating the same with a matrix resin 3 and then curing the matrix resin 3. The whole contains several tens of thousands to hundreds of thousands of carbon fibers (single fibers, filaments) 2. In the carbon fiber composite cable 1, the volume ratio (fiber volume content) V f of the carbon fibers 2 in the entire volume is generally 30% or more and less than 85%.

　炭素繊維複合材ケーブル１は，たとえば12,000本程度の炭素繊維２を束ねたトウを６本～７本程度束ね，これにマトリックス樹脂３を含浸して硬化させることでつくられる。炭素繊維複合材ケーブル１は，図示するようにそこに含まれるすべての炭素繊維２を長手方向に一方向に引き揃えたものであってもよいし，複数のトウを撚り合わせたものであってもよい。長手方向に一方向にのびる１本のトウ（心線）とその周囲に撚り合わせた複数本のトウ（側線）とから，炭素繊維複合材ケーブル１を構成してもよい。炭素繊維複合材ケーブル１を構成する炭素繊維２の本数によって炭素繊維複合材ケーブル１の直径は任意に調整することができる。 The carbon fiber composite cable 1 is produced, for example, by bundling about 6 to 7 tows in which about 12,000 carbon fibers 2 are bundled, impregnating the tow with the matrix resin 3 and curing it. The carbon fiber composite cable 1 may be one in which all the carbon fibers 2 contained therein are aligned in one direction in the longitudinal direction as illustrated, or a plurality of tows are twisted together. It is also good. The carbon fiber composite cable 1 may be configured of one tow (core wire) extending in one direction in the longitudinal direction and a plurality of tow (lateral lines) twisted around the one. The diameter of the carbon fiber composite cable 1 can be arbitrarily adjusted by the number of carbon fibers 2 constituting the carbon fiber composite cable 1.

　マトリックス樹脂３は，熱可塑性樹脂に対して以下に示すオリゴマーを混合したもので，これによってマトリックス樹脂３の粘度を，母材である熱可塑性樹脂の粘度よりも低下させて流動性を高めたものである。母材の熱可塑性樹脂には，ポリフェニレンサルファイド，ポリフェニレンエーテル，フッ素含有樹脂（四フッ化エチレンなど），アミド基含有樹脂（ポリアミドなど）を用いることができる。混合されるオリゴマーには，フェノール性水酸基を有する有機化合物（たとえばノボラック型フェノール樹脂）とグリジシルエーテル基を有する有機化合物（たとえばフェニルグリシジルエーテル）とを反応させて得られるものが用いられる。 The matrix resin 3 is a mixture of a thermoplastic resin and an oligomer shown below, whereby the viscosity of the matrix resin 3 is made lower than the viscosity of the thermoplastic resin as the base material to improve the fluidity. It is. For the thermoplastic resin of the base material, polyphenylene sulfide, polyphenylene ether, fluorine-containing resin (such as tetrafluoroethylene), and amide group-containing resin (such as polyamide) can be used. As an oligomer to be mixed, one obtained by reacting an organic compound having a phenolic hydroxyl group (for example, a novolak type phenol resin) and an organic compound having a glycidyl ether group (for example, a phenyl glycidyl ether) is used.

　マトリックス樹脂３は常温において固体であり，熱を加えることで溶融し，冷却することで固化するので，熱可塑性樹脂と言うことができるが，マトリックス樹脂３を得るために用いられる母材としての熱可塑性樹脂（ポリフェニレンサルファイドなど）とは少なくとも粘度において区別される。マトリックス樹脂３を得るための母材としての熱可塑性樹脂の粘度はメルトフローレートにおいて10ｇ／10min～30ｇ／10min程度であり，マトリックス樹脂３の粘度はこれよりも遙かに低い粘度を持つ。 The matrix resin 3 is solid at normal temperature, melts by applying heat, and solidifies by cooling, so it can be said to be a thermoplastic resin, but it can be said as a thermoplastic resin. It is distinguished at least in viscosity from plastic resins (such as polyphenylene sulfide). The viscosity of the thermoplastic resin as a base material for obtaining the matrix resin 3 is about 10 g / 10 min to 30 g / 10 min in melt flow rate, and the viscosity of the matrix resin 3 is much lower than this.

　上述したオリゴマーには重量平均分子量10,000未満のものが用いられる。重量平均分子量が10,000を超えると，熱可塑性樹脂とオリゴマーとの相溶性が低下するからである。もっとも，相溶性を重視する場合には重量平均分子量 5,000以下のオリゴマーを用いるのが好ましい。オリゴマーの重量平均分子量は典型的には温度管理によって調整することができる。 As the above-mentioned oligomer, one having a weight average molecular weight of less than 10,000 is used. When the weight average molecular weight exceeds 10,000, the compatibility between the thermoplastic resin and the oligomer decreases. However, when importance is attached to compatibility, it is preferable to use an oligomer having a weight average molecular weight of 5,000 or less. The weight average molecular weight of the oligomers can typically be adjusted by temperature control.

　図３は，繊維体積含有率Ｖｆが50％，直径が 2.5mmの炭素繊維複合材ケーブル１（以下，被試験体という）の引張破断強度試験の結果をグラフによって示している。図３において，横軸はマトリックス樹脂３に含まれるオリゴマーの濃度（単位はwt％）を，縦軸は被試験体の引張破断強度（単位はkN／mm2 ）をそれぞれ示している。被試験体は，粉末状のマトリックス樹脂３を炭素繊維製のトウに付着させ，マトリックス樹脂３が付着した６本のトウを 330℃に加熱した引抜ダイスに集めて集束することで炭素繊維束とし，かつ加熱によってマトリックス樹脂３を溶融し，引抜ダイスから引抜くことで作成した。引抜ダイスにおいて炭素繊維束にマトリックス樹脂３が含浸する。粉末状のマトリックス樹脂３をトウに付着させるのに代えて，あらかじめ溶融させたマトリックス樹脂３をトウに付着させてもよいし，繊維状にしたマトリックス樹脂３をトウとともに束にしてもよい。なお，オリゴマーを混合していない熱可塑性樹脂を含浸させた炭素繊維複合材ケーブルも作成し，これについても比較のために引張破断強度試験を行った。 FIG. 3 is a graph showing the results of a tensile breaking strength test of a carbon fiber composite cable 1 (hereinafter referred to as a test object) having a fiber volume content V f of 50% and a diameter of 2.5 mm. In FIG. 3, the horizontal axis shows the concentration (unit: wt%) of the oligomer contained in the matrix resin 3, and the vertical axis shows the tensile breaking strength of the test object (unit: kN / mm 2 ). The test sample is made by adhering powdery matrix resin 3 to a carbon fiber tow, collecting the six tow with the matrix resin 3 adhered on a drawing die heated to 330 ° C. to form a carbon fiber bundle. , And the matrix resin 3 was melted by heating and drawn from a drawing die. The matrix resin 3 impregnates the carbon fiber bundle at the drawing die. Instead of attaching the powdered matrix resin 3 to the tow, the matrix resin 3 melted in advance may be attached to the tow, or the fibrous matrix resin 3 may be bundled with the tow. In addition, a carbon fiber composite cable impregnated with a thermoplastic resin not mixed with an oligomer was also prepared, and a tensile breaking strength test was also conducted for comparison.

　図４は，マトリックス樹脂３に含まれるオリゴマーの濃度（単位はwt％）とマトリックス樹脂３のメルトフローレート（ＭＦＲ）（単位はｇ／10min ）の関係を示すグラフである。メルトフローレートはJIS K 7210の手順に沿って測定した。オリゴマーを混合していない熱可塑性樹脂のメルトフローレートも測定した。メルトフローレートは試料の粘度を表す指標として用いることができ，メルトフローレートが高いほど試料の粘度が低く（流動しやすい），低いほど試料の粘度は高い（流動しにくい）。 FIG. 4 is a graph showing the relationship between the concentration of oligomers contained in the matrix resin 3 (unit: wt%) and the melt flow rate (MFR) (unit: g / 10 min) of the matrix resin 3. Melt flow rate was measured according to the procedure of JIS K 7210. The melt flow rate of the thermoplastic resin not mixed with the oligomer was also measured. The melt flow rate can be used as an index indicating the viscosity of the sample, the higher the melt flow rate, the lower the viscosity of the sample (the more easily it flows), and the lower the viscosity, the higher the viscosity of the sample (the less flowable).

　具体的には，熱可塑性樹脂にはポリフェニレンエーテル樹脂（東ソー株式会社製）を用いた。また，オリゴマーには，ノボラック型フェノール樹脂（旭有機材株式会社製）にフェニルグリシジルエーテル（東京化成工業株式会社製）を反応させて安定化させたものを採用した。所定の温度条件のもとでノボラック型フェノール樹脂とフェニルグリシジルエーテルを反応させたところ，オリゴマーの重量平均分子量を10,000未満とすることができた。 Specifically, polyphenylene ether resin (manufactured by Tosoh Corporation) was used as the thermoplastic resin. Further, as the oligomer, one obtained by reacting and stabilizing novolac type phenol resin (manufactured by Asahi Organic Materials Co., Ltd.) with phenyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was adopted. When novolak type phenol resin and phenyl glycidyl ether were reacted under predetermined temperature conditions, it was possible to make the weight average molecular weight of the oligomer less than 10,000.

　図４のグラフを参照して，ポリフェニレンエーテル樹脂に上述のオリゴマーを混合することで得られるマトリックス樹脂３は，メルトフローレートが確実に上昇すること（粘度が低下すること），さらに混合するオリゴマーの量を増やすことでメルトフローレートは急激に上昇することが確認された。すなわち，上述のオリゴマーを熱可塑性樹脂に混合したマトリックス樹脂３はその粘度が確実に低下する。 Referring to the graph of FIG. 4, the matrix resin 3 obtained by mixing the above-described oligomer with the polyphenylene ether resin is that the melt flow rate is surely increased (the viscosity is decreased), and the mixed polymer is It was confirmed that the melt flow rate rises sharply by increasing the amount. That is, the viscosity of the matrix resin 3 in which the above-described oligomer is mixed with the thermoplastic resin is surely reduced.

　図３のグラフを参照して，熱可塑性樹脂を炭素繊維束に含浸させたケーブル（オリゴマー濃度が０wt％のもの）に比べて，マトリックス樹脂３を炭素繊維束に含浸させたケーブルは，引張破断強度を向上させることができることが確認された。マトリックス樹脂３は，図４を参照して説明したように，熱可塑性樹脂に比べて粘度が低く，したがってマトリックス樹脂３（マトリックス樹脂に含まれる熱可塑性樹脂）を，炭素繊維束に十分に含浸させることができるためであると考えられる。炭素繊維束にマトリックス樹脂３が十分に含侵されることで，多数本の繊維がマトリックス樹脂３によって強固に把持され，ケーブル内にボイドが発生しにくくなり，これによってケーブルの機械的強度の向上が発現する。また，引張破断強度が十分に上昇していることから，上述したオリゴマーは熱可塑性樹脂の分子量を少なくとも大きく低下させるものではないと考えられる。 Referring to the graph of FIG. 3, the cable in which the carbon fiber bundle is impregnated with the matrix resin 3 has a tensile fracture compared to the cable in which the carbon fiber bundle is impregnated with the thermoplastic resin (in which the oligomer concentration is 0 wt%). It was confirmed that the strength could be improved. As described with reference to FIG. 4, the matrix resin 3 has a lower viscosity than the thermoplastic resin, and hence the carbon fiber bundle is sufficiently impregnated with the matrix resin 3 (thermoplastic resin contained in the matrix resin). It is thought that it is because it can. By sufficiently impregnating the carbon fiber bundle with the matrix resin 3, a large number of fibers are firmly held by the matrix resin 3, and voids are less likely to be generated in the cable, whereby the mechanical strength of the cable is improved. It is expressed. Further, it is considered that the above-mentioned oligomers do not at least greatly reduce the molecular weight of the thermoplastic resin, because the tensile strength at break is sufficiently increased.

　図３のグラフを参照して，マトリックス樹脂３に占めるオリゴマーの濃度を増加させ続けると，被試験体の引張破断強度は減少に転じ，およそ30wt％の濃度において，マトリックス樹脂３を含浸させた炭素繊維束からつくられるケーブルの引張破断強度は，熱可塑性樹脂を含浸させた炭素繊維束からつくられる従来のケーブルの引張破断強度（オリゴマー濃度が０wt％のもの）とほぼ同じとなることも確認された。図４に示すように，オリゴマーの濃度を増やすことでマトリックス樹脂３のメルトフローレートが急激に上昇しており，マトリックス樹脂３の粘度が低くなりすぎることで，炭素繊維束からマトリックス樹脂３が落下する量が多くなったり，熱可塑性樹脂の希釈化が生じるためであると考えられる。従来のケーブルと同等以上の引張破断強度を発揮させるためには，オリゴマーの濃度を30wt％未満にとどめることが必要である。 Referring to the graph of FIG. 3, when the concentration of the oligomer occupied in matrix resin 3 is continued to increase, the tensile breaking strength of the test sample turns to decrease, and carbon impregnated with matrix resin 3 at a concentration of about 30 wt% It was also confirmed that the tensile strength at break of cables made from fiber bundles is almost the same as that of conventional cables made from carbon fiber bundles impregnated with thermoplastic resin (with an oligomer concentration of 0 wt%) The As shown in FIG. 4, the melt flow rate of the matrix resin 3 is rapidly increased by increasing the concentration of the oligomers, and the viscosity of the matrix resin 3 is too low, so that the matrix resin 3 falls from the carbon fiber bundle. It is believed that this is because the amount to be added is increased or the dilution of the thermoplastic resin occurs. In order to exert a tensile strength equal to or higher than that of the conventional cable, it is necessary to keep the concentration of the oligomer to less than 30 wt%.

　好ましくは，熱可塑性樹脂のメルトフローレートの 1.5～50倍向上したメルトフローレートを持つマトリックス樹脂３が用いられる。マトリックス樹脂３のメルトフローレートを熱可塑性樹脂のメルトフローレートから 1.5倍以上高めることによって，上述した引抜工程におけるケーブル表面の炭素繊維２の切れ（粗れ）を防止することができ，また集束工程（複数本のトウを一つに束ね，マトリックス樹脂３を含浸する工程）を容易にすることができる。マトリックス樹脂３のメルトフローレートを熱可塑性樹脂のメルトフローレートから50倍以上高めないようにすることで，ケーブルの引張強度を従来ケーブルと少なくとも同等に維持することができる。 Preferably, a matrix resin 3 having a melt flow rate improved 1.5 to 50 times the melt flow rate of the thermoplastic resin is used. By increasing the melt flow rate of the matrix resin 3 by 1.5 times or more from the melt flow rate of the thermoplastic resin, it is possible to prevent breakage (roughness) of the carbon fibers 2 in the cable surface in the above-described drawing process, and (The step of bundling a plurality of tows into one and impregnating the matrix resin 3) can be facilitated. By not increasing the melt flow rate of the matrix resin 3 by 50 times or more from the melt flow rate of the thermoplastic resin, the tensile strength of the cable can be maintained at least equal to that of the conventional cable.

　１　炭素繊維複合材ケーブル
　２　炭素繊維
　３　マトリックス樹脂 1 carbon fiber composite cable 2 carbon fiber 3 matrix resin

Claims (9)

　高強度繊維の束にマトリックス樹脂を含浸させた高強度繊維複合材ケーブルであって，
　上記マトリックス樹脂が，熱可塑性樹脂に，フェノール性水酸基を有する有機化合物とグリジシルエーテル基を有する有機化合物とを反応させて得られる重量平均分子量10,000未満のオリゴマーを混合させたものであることを特徴とする，
　高強度繊維複合材ケーブル。 A high strength fiber composite cable in which a bundle of high strength fibers is impregnated with a matrix resin,
The matrix resin is characterized in that a thermoplastic resin is mixed with an oligomer having a weight average molecular weight of less than 10,000 obtained by reacting an organic compound having a phenolic hydroxyl group and an organic compound having a glycidyl ether group. The,
High strength fiber composite cable. 　30wt％未満の上記オリゴマーが混合されている，
　請求項１に記載の高強度繊維複合材ケーブル。 Less than 30 wt% of the above oligomers are mixed,
A high strength fiber composite cable according to claim 1. 　上記熱可塑性樹脂がポリフェニレンサルファイドである，
　請求項１または２に記載の高強度繊維複合材ケーブル。 The thermoplastic resin is polyphenylene sulfide,
A high strength fiber composite cable according to claim 1 or 2. 　上記熱可塑性樹脂がポリフェニレンエーテルである，
　請求項１または２に記載の高強度繊維複合材ケーブル。 Said thermoplastic resin is polyphenylene ether,
A high strength fiber composite cable according to claim 1 or 2. 　上記熱可塑性樹脂がフッ素含有樹脂である，
　請求項１または２に記載の高強度繊維複合材ケーブル。 The thermoplastic resin is a fluorine-containing resin,
A high strength fiber composite cable according to claim 1 or 2. 　上記熱可塑性樹脂がアミド基含有樹脂である，
　請求項１または２に記載の高強度繊維複合材ケーブル。 The thermoplastic resin is an amide group-containing resin,
A high strength fiber composite cable according to claim 1 or 2. 　上記高強度繊維が炭素繊維である，
　請求項１から６のいずれか一項に記載の高強度繊維複合材ケーブル。 The high strength fiber is carbon fiber,
The high strength fiber composite cable according to any one of claims 1 to 6. 　繊維体積含有率が30％以上85％未満である，
　請求項１から７のいずれか一項に記載の高強度繊維複合材ケーブル。 Fiber volume content is more than 30% and less than 85%,
A high strength fiber composite cable according to any one of the preceding claims. 　熱可塑性樹脂に，フェノール性水酸基を有する有機化合物とグリジシルエーテル基を有する有機化合物とを反応させて得られる重量平均分子量10,000未満のオリゴマーを所定量混合することによってつくられる，上記熱可塑性樹脂のメルトフローレートよりも 1.5～50倍向上したメルトフローレートを持つマトリックス樹脂を加熱して溶融し，
　溶融したマトリックス樹脂を高強度繊維の束に含浸し，
　マトリックス樹脂が含浸した高強度繊維の束を引抜成形する，
　高強度繊維複合材ケーブルの製造方法。 The thermoplastic resin of the above thermoplastic resin produced by mixing a predetermined amount of an oligomer having a weight-average molecular weight of less than 10,000 obtained by reacting an organic compound having a phenolic hydroxyl group and an organic compound having a glycidyl ether group with a thermoplastic resin Heating and melting a matrix resin having a melt flow rate which is 1.5 to 50 times better than the melt flow rate,
Impregnating the molten matrix resin into a bundle of high strength fibers,
Drawing out a bundle of high strength fibers impregnated with matrix resin,
Method of manufacturing high strength fiber composite cable.
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EP3660209A1 (en) 2020-06-03
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